TWI415879B - Thermal curing polyimide silicon resin composition - Google Patents

Abstract

A heat-curable polyimide silicone resin composition comprising 100 parts by weight of a polyimide silicone resin having a radically polymerizable group bonded to a silicon atom, 0.1 to 20 parts by weight of a peroxycarbonate curing agent, and a solvent. The composition can be cured at a low temperature in a short time.

Description

Thermosetting polyamidoxime resin composition

The present invention relates to a thermosetting polyimine oxime resin composition, and more particularly to a polyetherimide lanthanide composition containing a radical polymerizable group, the composition being composed of a predetermined hardener The combination is cured at a relatively low temperature and in a short period of time, and provides a cured film excellent in heat resistance, mechanical strength, flexibility, solvent resistance, and adhesion to various substrates.

Polyimide resin is widely used as a printed circuit board, a heat-resistant adhesive tape, an electrical component, a protective film of a semiconductor material, an interlayer insulating film, and the like because of its high heat resistance and excellent electrical insulating properties. However, the polyimine resin is only soluble in a limited amount of solvent, so that workability is sometimes poor. Therefore, the following method is employed: a method in which a polylysine which is more soluble in various organic solvents is coated on a substrate, and dehydration cyclization is carried out by a high temperature treatment to obtain a polyimide resin. However, in this method, it is necessary to perform high-temperature and long-time heating, and thus it is easy to cause thermal deterioration of the substrate. On the other hand, if the heating is insufficient, the polyamine acid remains in the structure of the obtained resin, resulting in a decrease in moisture resistance, corrosion resistance, and the like.

Therefore, it is known to apply a solution of a polyimine resin which is soluble in an organic solvent to a substrate instead of polylysine, and then volatilize the solvent by heating to form a film of a polyimide film (for example) Japanese Patent Laid-Open No. 2-23632). However, the resin film obtained by using the above-mentioned organic solvent-soluble polyimine resin has poor solvent resistance. Therefore, some people have proposed A heat-curable polyimine oxime which is soluble in an organic solvent and has a polymerizable side chain (for example, Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. The resin described in Japanese Laid-Open Patent Publication No. Hei 2-147730 can be cured by any of a thermal method and a light method. The resin described in Japanese Laid-Open Patent Publication No. Hei 7-268098 is cured by hydroformylation with an organohydroquinone, but it takes 5 hours to cure.

Accordingly, it is an object of the present invention to provide a polyimide composition which is hardened at a relatively low temperature and for a short period of time.

As a result of various studies, the present inventors have found that the above object can be attained by combining a polyalkylenimine resin containing a radical polymerizable group with a specific curing agent. That is, the present invention relates to a thermosetting polyimine oxime resin composition comprising: 100 parts by weight of a polyamidoxime resin containing a radical polymerizable group bonded to a ruthenium atom, 0.1 to 20 parts by weight A peroxycarbonate hardener and a solvent, wherein the resin component in the thermosetting polyimine resin composition is composed of a polyimide resin.

The composition of the present invention is in the form of a solution compatible with various organic solvents, and is excellent in handleability. Further, the composition of the present invention can form a hardened film by a low temperature and short time heat treatment. The obtained cured film is excellent in heat resistance, mechanical strength, solvent resistance, and adhesion to various substrates.

The above and other objects, features and advantages of the present invention will become more <RTIgt; See below.

In the resin composition of the present invention, the radical polymerizable group bonded to the ruthenium atom in the polyamidoxime resin is hardened in the presence of peroxycarbonate. Thereby, rapid hardening at low temperatures can be achieved. Examples of the radical polymerizable group include a vinyl group, a propylene group, a (meth) propylene oxypropyl group, a (meth) propylene oxy oxyethyl group, a (meth) propylene fluorenyloxymethyl group, and a benzene group. Vinyl and the like. Among the above groups, a vinyl group is preferred from the viewpoint of easily obtaining a raw material. The radical polymerizable group may be present at any of the end portion, the central portion, or the like as long as it is a fluorene moiety of the polyimine oxime resin.

The peroxycarbonate used in the present invention may, for example, be a tertiary butyl peroxyisopropyl carbonate, a third-stage butyl peroxy 2-ethylhexyl carbonate, or a third-grade pentylperoxy 2- Monoperoxycarbonate such as ethylhexyl carbonate; bis(2-ethylhexyl)peroxydicarbonate, 1,6-bis(tertiary butylperoxycarbonyloxy)hexane, bis(4- Tertiary butylcyclohexyl)peroxydicarbonate, bis(2-ethoxyethyl)peroxydicarbonate, di(n-propyl)peroxydicarbonate, diisopropylperoxydicarbonate Ester and the like. Of these, preferred are tertiary butyl peroxy 2-ethylhexyl carbonate, tertiary pentyl peroxy 2-ethylhexyl carbonate, and 1,6-bis (third butyl peroxycarbonyl) Oxy)hexane, bis(4-tert-butylcyclohexyl)peroxydicarbonate. The above peroxycarbonate has good compatibility with the polyimine resin of the present invention and achieves rapid hardening at a low temperature.

The amount of the peroxycarbonate is 0.1 to 20 parts by weight, preferably 1 to 10 parts by weight, per 100 parts by weight of the polyamidoxime resin. Preservation of the composition of the present invention if the amount of peroxycarbonate added exceeds the above upper limit The stability and the high temperature and high humidity resistance of the hardened material tend to decrease. On the other hand, when the amount of peroxycarbonate added is less than the above lower limit, the cured product has poor solvent resistance.

The solvent in the composition of the present invention may be any solvent that can dissolve the polyimine oxime resin and the peroxycarbonate. Examples of suitable solvents include ethers such as tetrahydrofuran and anisole; ketone solvents such as cyclohexanone, 2-butanone, methyl isobutyl ketone, 2-heptanone, 2-octanone, and acetophenone. An ester solvent such as butyl acetate, methyl benzoate or γ-butyrolactone; a cellosolve solvent such as butyl cellosolve acetate or propylene glycol monomethyl ether acetate; N,N-dimethylformamide a guanamine-based solvent such as N,N-dimethylacetamide or N-methyl-2-pyrrolidone; and an aromatic hydrocarbon solvent such as toluene or xylene; preferably a ketone solvent or an ester solvent; The cellosolve is a solvent. The above solvents may be used singly or in combination of two or more kinds. The amount of the solvent is preferably adjusted depending on the solubility of the resin, the workability at the time of coating, the thickness of the desired coating, and the like, and the concentration of the polyimide resin is usually from 1 to 50% by weight ( Used within the range of wt%). Alternatively, a higher resin concentration is first prepared when the composition is stored, and can be diluted to the desired concentration when used.

Preferably, the polyimine oxime resin contains two kinds of repeating units represented by the following formula (1).

The above formula is a composition. That is, k and m represent the content ratios of the repeating unit including A and the repeating unit including B. k is 0≦k≦1, m is 0<m≦1 number, k+m=1. As described below, B is an anthracene residue and contains a radical polymerizable group. Each constituent unit can be randomly combined.

X in the formula (1) is any one of the following tetravalent groups.

A in the formula (1) is a divalent group represented by the following formula (2).

In the above formula (2), D independently of each other represents any one of the following divalent organic groups. e, f, g are 0 or 1.

-CH ₂ -, -O-, -SO ₂ -, -CONH-, , ,

The group represented by the formula (2) includes the following groups.

In the formula (1), B is represented by the following formula (3).

In the formula (3), R ¹ independently represents a monovalent hydrocarbon group having 1 to 8 carbon atoms, and examples thereof include an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group and a hexyl group; a cycloalkyl group such as a cyclohexyl group; an aryl group such as a phenyl group; an aralkyl group such as a benzyl group or a phenethyl group; and the like. From the viewpoint of easily obtaining a raw material, a methyl group, an ethyl group, or a phenyl group is preferred. R ² is the above-mentioned radical polymerizable group.

a is an integer of 0 to 100, preferably an integer of 3 to 70. b is an integer from 1 to 100, preferably an integer from 3 to 70, and more preferably an integer from 5 to 50.

The polyiminoimine resin of the formula (1) has a polystyrene-equivalent weight average molecular weight of 5,000 to 150,000, preferably 8,000 to 100,000. The polyimide film having a molecular weight of less than the above lower limit has a low strength of the obtained film. And The polyimine resin having a sub-quantity exceeding the above upper limit lacks compatibility with a solvent and is difficult to handle.

Polyimine oxime resins can be prepared by conventional methods. First, an acid dianhydride for deriving X, a diamine for deriving A, and a diamine polyoxyalkylene for deriving B are added to a solvent to be reacted at a low temperature, that is, at a temperature of from 20 ° C to 50 ° C. , a precursor polyamine which is a precursor of a polyimide resin. Next, the obtained polyaminic acid solution is preferably heated to 80 ° C ~ 200 ° C, particularly preferably heated to 140 ° C ~ 180 ° C, the polyamine acid guanamine is subjected to dehydration ring closure reaction, thereby obtaining poly A solution of a quinone imine resin. The solution is poured into a solvent such as water, methanol, ethanol or acetonitrile to precipitate a reaction product, and the precipitate is dried to obtain a polyimine oxime resin.

Among them, the total ratio of the diamine and the diamine polyoxymethane to the tetracarboxylic dianhydride is calculated by the molar ratio, preferably 0.95 to 1.05, particularly preferably 0.98 to 1.02. Moreover, examples of the solvent used in the production of the polyimine oxime resin include N-methyl-2-pyrrolidone, cyclohexanone, γ-butyrolactone, and N,N-dimethylacetamide. . Further, by using an aromatic hydrocarbon such as toluene or xylene in combination, it is also possible to easily use azeotropic removal of water generated during the imidization. The above solvents may be used singly or in combination of two or more kinds.

In addition, in order to adjust the molecular weight of a polythenimine oxime resin, the monofunctional raw material, such as a phthalic anhydride and an aniline, can also be added. At this time, the amount of the above-mentioned monofunctional base material to be added is preferably 10 mol% or less with respect to the polyamidoxime resin.

Further, in the imidization process, a method in which ruthenium imidization is carried out by adding a dehydrating agent and a ruthenium amide catalyst, and heating to about 50 ° C as needed may be employed. In the above method, as the dehydrating agent, for example, an acid anhydride such as acetic anhydride, propionic anhydride or trifluoroacetic anhydride can be used. The amount of the dehydrating agent used is preferably from 1 to 10 moles per 1 mole of the diamine. As the ruthenium amide catalyst, for example, a third-grade amine such as pyridine, trimethylpyridine, lutidine or triethylamine can be used. The ruthenium imidization catalyst is preferably used in an amount of from 0.5 to 10 moles per mole of the dehydrating agent used.

In the case of using at least one of a diamine and a tetracarboxylic dianhydride, the reaction method is not particularly limited, and examples thereof include a method in which all the raw materials are mixed in advance and co-condensed, or two types used. Or a method in which two or more kinds of diamine or tetracarboxylic dianhydride are separately reacted while being sequentially added.

As the acid dianhydride for derivatizing X, there may be mentioned 3,3',4,4'-diphenylphosphonium tetracarboxylic dianhydride, 3,3',4,4'-biphenyltetracarboxylic acid Anhydride, 2,3',3,4'-biphenyltetracarboxylic dianhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexene 1,2-dicarboxylic anhydride, 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride, 1,2,3 , 4-butane tetracarboxylic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 4,4'-hexafluoropropylenediphthalic dianhydride, 2 , 2'-bis(p-trimethoxyphenyl)propane, 1,3-tetramethyldioxane diphthalic dianhydride, 4,4'-oxydi-n-alk Phthalic anhydride.

Examples of the diamine used for the derivatization A include 4,4′-diaminobenzimidamide, 4,4′-diaminodiphenyl ether, and 3,4′-diaminodiphenyl ether. 4,4'- Diaminodiphenyl hydrazine, 3,3'-dimethyl-4,4'-diaminobiphenyl, 4,4'-(p-phenylene diisopropylidene)diphenylamine, 4,4' -(m-phenylene diisopropylidene)diphenylamine, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 1,3 - bis(3-aminophenoxy)benzene, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy) Phenyl]hexafluoropropane, bis[4-(4-aminophenoxy)phenyl]indole, bis[4-(3-aminophenoxy)phenyl]anthracene, 4,4'- Bis(4-aminophenoxy)biphenyl, 9,9'-bis(4-aminophenyl)anthracene, and the like.

As the diaminopolyoxyalkylene to be used for the derivatization B, a diaminopolyoxyalkylene having an amine group bonded to both ends of the above formula (3) can be used.

The composition of the present invention can be obtained by mixing the polyimine oxime resin and peroxycarbonate obtained in this manner with a solvent by a conventional method such as a mixer. In the above composition, a cautionary additive, for example, a decane coupling agent for improving adhesion to a substrate, may be added to the extent that the object of the present invention is not inhibited.

When the composition contains a solvent having a low boiling point, the composition is applied onto a substrate, and then the solvent is volatilized, and then heated at a temperature of about 80 to 200 ° C for 0.5 to 2 hours to remove the solvent. Can be hardened. Therefore, the above composition is suitable as a coating agent for applying a film to a substrate having low heat resistance or a material which is deteriorated by heat. Further, since a cured film is easily obtained without using a special device for irradiating light, it is considered that the above-described composition contributes to improvement in workability and resource saving.

Example

Hereinafter, the examples are given to further illustrate the invention, but the invention is not limited to the examples.

Synthesis of polyamidiamine oxime resin [Synthesis Example 1]

Into a flask equipped with a stirrer, a thermometer and a nitrogen exchange device, 71.6 g (0.2 mol) of 3,3',4,4'-diphenylphosphonium tetracarboxylic dianhydride and 350 g of cyclohexanone were placed. Then, while adjusting the temperature of the reaction system to not more than 50 ° C, 87.6 g (0.1 mol) of the diamino vinyl fluorene represented by the following formula (4) and 41.1 g were added dropwise to the flask. A solution of (0.1 mol) of 2,2-bis[4-(4-aminophenoxy)phenyl]propane dissolved in 100 g of cyclohexanone. After the completion of the dropwise addition, the mixture was further stirred at room temperature for 10 hours. Next, a reflux condenser equipped with a moisture storage device was attached to the flask, followed by the addition of 50 g of xylene, the temperature was raised to 150 ° C, and the temperature was maintained for 6 hours to obtain a yellow-brown solution. The solution thus obtained was cooled to room temperature (25 ° C), and then poured into methanol, and the obtained precipitate was dried to obtain a polyfluorene containing repeating units represented by the following formulas (5-1) and (5-2). Imine resin.

When the infrared absorption spectrum of the obtained resin was measured, absorption from unreacted polyaminic acid did not occur, and absorption from the imine group was confirmed at 1,780 cm ^-1 and 1,720 cm ^-1 . When the weight average molecular weight (in terms of polystyrene) of the resin was measured by gel permeation chromatography (GPC) using tetrahydrofuran as a solvent, the weight average molecular weight was 34,000. This resin was used as a polyimine oxime resin (a).

[Synthesis Example 2]

In a flask equipped with a stirrer, a thermometer, and a nitrogen displacement device, 88.8 g (0.2 mol) of 4,4'-hexafluoropropylenediphthalic dianhydride and 550 g of cyclohexanone were placed. Then, while adjusting the temperature of the reaction system to not more than 50 ° C, 192.2 g (0.06 mol) of the diamino vinyl fluorene represented by the following formula (6) and 40.9 g were added dropwise to the flask. A solution of (0.14 mol) of 1,3-bis(3-aminophenoxy)benzene dissolved in 200 g of cyclohexanone. After the completion of the dropwise addition, the mixture was further stirred at room temperature for 10 hours. Next, a reflux condenser equipped with a moisture storage device was attached to the flask, and then 70 g of xylene was added thereto, and the temperature was raised to 150 ° C, and the temperature was maintained for 6 hours to obtain yellow. Brown solution. The solution obtained in this manner was cooled to room temperature (25 ° C), and then poured into methanol, and the obtained precipitate was dried to obtain a polyfluorene containing repeating units represented by the following formulas (7-1) and (7-2). Imine resin.

When the infrared absorption spectrum of the obtained resin was measured, absorption from unreacted polyaminic acid did not occur, and absorption from the imine group was confirmed at 1,780 cm ^-1 and 1,720 cm ^-1 . When the weight average molecular weight of the resin was measured in the same manner as in Synthesis Example 1, the weight average molecular weight was 42,000. This resin was used as a polyamidoxime resin (b).

[Synthesis Example 3]

In a flask equipped with a stirrer, a thermometer, and a nitrogen displacement device, 62.0 g (0.2 mol) of hydroxydiphthalic dianhydride and 400 g of n-methyl-2-pyrrolidone were placed. Then, while adjusting the temperature of the reaction system to not more than 50 ° C, 102 g (0.06 mol) of the diamino vinyl fluorene represented by the following formula (8) and 57.5 g (d) were added dropwise to the flask. 0.14 moles) A solution of 2,2-bis[4-(4-aminophenoxy)phenyl]propane dissolved in 100 g of cyclohexanone. After the completion of the dropwise addition, the mixture was further stirred at room temperature for 10 hours. Next, a reflux condenser equipped with a moisture storage device was attached to the flask, and then 70 g of xylene was added thereto, and the temperature was raised to 150 ° C, and the temperature was maintained for 6 hours to obtain a yellow-brown solution. The solution thus obtained is cooled to room temperature (25 ° C), and then introduced into methanol, and the obtained precipitate is dried to obtain a polyimine oxime resin represented by the following formulas (9-1) and (9-2). .

When the infrared absorption spectrum of the obtained resin was measured, absorption from unreacted polyaminic acid did not occur, and absorption from the imine group was confirmed at 1,780 cm ^-1 and 1,720 cm ^-1 . When the weight average molecular weight of the resin was measured in the same manner as in Synthesis Example 1, the weight average molecular weight was 35,000. This resin was used as a polyamidoxime resin (c).

[Synthesis Example 4]

A free radical polymerizable group-free polyimine oxime resin for comparison was prepared.

Into a flask equipped with a stirrer, a thermometer and a nitrogen displacement device, 71.6 g (0.2 mol) of 3,3'4,4'-diphenylphosphonium tetracarboxylic dianhydride and 350 g of cyclohexanone were placed. Then, while adjusting the temperature of the reaction system to not more than 50 ° C, 84.0 g (0.6 mol) of the diamine oxirane represented by the following formula (10) and 50 g (0.1 mol) were added dropwise to the flask. A solution of 2,2-bis[4-(4-aminophenoxy)phenyl]propane dissolved in 100 g of cyclohexanone. After the completion of the dropwise addition, the mixture was further stirred at room temperature for 10 hours. Next, a reflux condenser equipped with a moisture storage device was attached to the flask, followed by the addition of 50 g of xylene, the temperature was raised to 150 ° C, and the temperature was maintained for 6 hours to obtain a yellow-brown solution. The solution obtained in this manner was cooled to room temperature (25 ° C), and then poured into methanol, and the obtained precipitate was dried to obtain a polyfluorene containing repeating units represented by the following formulas (11-1) and (11-2). Imine resin.

When the infrared absorption spectrum of the obtained resin was measured, absorption from unreacted polyaminic acid did not occur, and absorption from the imine group was confirmed at 1,780 cm ^-1 and 1,720 cm ^-1 . When the weight average molecular weight of the resin was measured in the same manner as in Synthesis Example 1, the weight average molecular weight was 30,000. This resin was used as a polyamidoxime resin (d).

Preparation of thermosetting resin composition

The polyimine oxime resin, the curing agent and the solvent shown in Table 1 were mixed at an addition ratio shown in the table to prepare a resin composition. It should be noted that “parts” in Table 1 means “parts by weight”. Further, the symbols in the column of the hardener in Table 1 indicate the following hardeners.

(I) Tertiary butyl peroxy-2-ethylhexyl carbonate

(II) 1,6-bis(tertiary butylperoxycarbonyloxy)hexane

(III) Tertiary pentylperoxy 2-ethylhexyl carbonate

(IV) bis(4-tert-butylcyclohexyl)peroxydicarbonate

(V) 1,1-bis(tertiary butylperoxy)-3,3,5-trimethylcyclohexane

(VI) cyclohexanone peroxide

(VII) Benzamidine peroxide

(VIII) butyl peroxyacetate

(IX) 1,1,3,3-tetramethylbutyl hydroperoxide

Formation of Hardened Film of Resin Composition and Its Performance Evaluation (1) Solvent resistance

Each of the obtained thermosetting resin compositions was applied onto a plate coated with a fluororesin to have a thickness of about 0.1 mm after drying, heated at 80 ° C for 30 minutes, and further heated at 150 ° C for 1 hour to form a polymer. The yttrium imide resin hardens the film. The obtained cured film was immersed in N-methyl-2-pyrrolidone (NMP) at room temperature for 30 minutes, and then the film was visually observed to be inflated. The results are shown in Table 2. Shown.

(2) Adhesiveness

The resin composition was applied onto a copper substrate, heated at 80 ° C for 30 minutes, and further heated at each final curing temperature shown in Table 1 for 1 hour to form a cured film. The adhesion of the obtained copper substrate with a cured film to a hardened film in a dryer at 150 ° C for 360 hours (as "heat-resistant adhesiveness") or saturation at 120 ° C and 2 atmospheres was evaluated by a square peeling test (JISK5400). Adhesion after 168 hours in water vapor (as "high temperature and high humidity adhesion"). The results are shown in Table 2. It should be noted that the numerical values (molecular/denominator) in Table 2 indicate the number of undrawn pieces (molecules) per 100 number of divisions (denominator). That is, 100/100 indicates no peeling at all, and 0/100 indicates total peeling.

(3) Mechanical strength

The compositions of Examples 2, 4 and Comparative Example 1 were each heated at 80 ° C for 30 minutes and further heated at 150 ° C for 1 hour, and the obtained cured product was measured for elongation and tensile strength in accordance with JIS K7113. The results are shown in Table 3.

As is clear from Table 2, compared with the composition of the comparative example lacking a hardening agent or a radical polymerizable property, and the reference example containing another peroxide, the poly(imine) and peroxycarbonic acid containing a radical-polymerizable group are included. The hardening property of the ester composition is remarkably high, and it is hardened by heating at a temperature of about 150 ° C to 180 ° C for several hours to form a hardening property excellent in solvent resistance, heat resistance, and mechanical properties. Things.

The composition of the present invention can be used as a protective film for an electric component, a semiconductor material, an interlayer insulating film, or an adhesive tape. It is particularly suitable for application to substrates having low heat resistance or materials which are deteriorated by heat.

While the present invention has been described in its preferred embodiments, the present invention is not intended to limit the invention, and the present invention may be modified and modified without departing from the spirit and scope of the invention. The scope of protection is subject to the definition of the scope of the patent application.

Claims (4)

A thermosetting polyimine oxime resin composition comprising: a polyimine oxime resin having a weight average molecular weight of 5,000 to 150,000 in terms of polystyrene, having two repeating units represented by the following formula (1) 100 parts by weight; a peroxycarbonate hardener, 0.1 to 20 parts by weight; and a solvent, wherein the resin component of the thermosetting polyimine resin composition is composed of the polyamidene resin , In the above formula (1), X is any one of the following tetravalent organic groups: A is expressed by the following formula (2): Wherein, in the above formula (2), D independently of each other represents any one of the following divalent organic groups; e, f, g is 0 or 1; -CH ₂ -, -O-, -SO ₂ -, -CONH-, , , B is expressed by the following formula (3): Wherein R ¹ independently of each other represents a substituted or unsubstituted monovalent hydrocarbon group having 1 to 8 carbon atoms, R ² is a radical polymerizable group, and a and b are each an integer of 1 or more and 100 or less; And k is 0≦k≦1, m is a number of 0<m≦1, and k+m=1. The thermosetting polyimine oxime resin composition according to claim 1, wherein R ² is a vinyl group. The thermosetting polyimine oxime resin composition according to claim 1, wherein the peroxycarbonate hardener is selected from the group consisting of a third-stage butylperoxy 2-ethylhexyl carbonate, a third-grade pentane Composition consisting of 2-ethylhexyl carbonate, 1,6-bis(tertiary butylperoxycarbonyloxy)hexane, bis(4-tert-butylcyclohexyl)peroxydicarbonate Group of people. The thermosetting polyimine oxime resin composition according to claim 1, wherein the solvent is selected from the group consisting of a ketone solvent, an ester solvent, and a cellosolve solvent.